The present application was filed on May 25, 2001 as international application serial number PCT/SE01/01178 and claims priority of Swedish patent application No. 0002230-1 filed on Jun. 15, 2000.
The present invention relates to the use of an amino compound, which is an esteramine or an amidoamine surfactant with improved biodegradability, as an adjuvant for agrochemically active compounds such as pesticides or fertilizers. The esteramines are obtained from an ethoxylated alcohol that has been carboxymethylated and then esterified with a tertiary hydroxyamine (alkanolamine), and the amidoamines are obtained by reaction between a fatty acid or a fatty acid methyl ester and a diamine, such as N,N-bishydroxyethyl-1,3-propylenediamine.
It is well known that the uptake as well as the efficacy of many pesticides and fertilizers can be improved by the addition of so called adjuvants. A variety of surfactants have been used for this purpose, and many of them are nitrogen containing. The surfactant group that has been most widely used in this connection is the fatty amine ethoxylates, but also other types of compounds have been described as adjuvants for pesticides or fertilizers. In EP-A1-0 638 236 is described an agricultural chemical composition containing as an adjuvant compounds of the esteramine type mentioned above. The esteramines disclosed in that publication all referred to compounds having two fatty alkyl chains. In WO 97/05779 plant protection compositions containing water-soluble active materials and one or more polyethoxylated amidoamines containing two carbon atoms between the amido and amino groups were claimed.
However, nowadays there is an increasing demand in most areas for compounds that are readily biodegradable. This is also the case within the agrochemical field, where adjuvants with a better biodegradability combined with a good ability to improve the uptake and efficacy of pesticides and fertilizers are being sought for. Thus, the purpose of the present invention is to provide adjuvants for pesticide formulations and for formulations containing fertilizers that are at least as effective as the prior used amino compounds. Another purpose is to provide adjuvants with an improved biodegradability compared to prior known amino compounds used as adjuvants.
It has now been found that compounds with the formula (I) 
where R1 is an aliphatic group containing 7-22 carbon atoms; EO is an ethyleneoxy group; Y is O or NH; R2 and R3 is independently xe2x80x94CH2CH2OH, xe2x80x94CH2CH(CH3)OH or an alkyl group with 1-5 carbon atoms, preferably 1-3 carbon atoms; n is a number between 0-10; x is a number 0 or 1 provided that when Y is O, then x is 1, and when Y is NH, then x is 0; and m is a number 2-6, preferably 2-3, provided that when Y is NH, then m is 3-6, preferably 3; or an adduct obtained by reacting one mole of the compound with 1-5 moles of an alkylene oxide having 2-3 carbon atoms; can be used as adjuvants in agrochemical compositions. When reacting the compound of formula I and an alkylene oxide having 2-3 carbon atoms, the alkylene oxide will be added to the groups containing active hydrogen atoms, and/or will be inserted into the ester or amide groups by rearrangement reactions. The compounds of the invention are readily biodegradable and are very effective in improving the efficacy of pesticides and fertilizers. Another benefit of the compounds is that they do not show any, or very little, eye irritancy. Some of the compounds can be formulated together with a pesticide or fertilizer, giving clear solutions of low viscosity, whereas others give solutions that are of moderate viscosity or turbid. These latter solutions often separate gradually into two phases. It has been found that also in these cases stable low-viscous solutions can be obtained by the addition of an alkyl glycoside according to the formula ROGp, where R is an alkyl group containing 6-10 carbon atoms, preferably 6-8, G is a monosaccharide residue and p is a number between 1-5. Surprisingly it has been found that the addition of an alkyl glycoside, besides giving rise to clear, stable solutions of low viscosity, also enhances the effect of the adjuvants of the invention. The alkyl glycosides are also readily biodegradable, so there is no disadvantage in adding them to the formulations.
Suitable examples of compounds according to the present invention are the esteramines described by the formula (II) 
where R4 is an alkyl group containing 8-22, preferably 8-18, carbon atoms, n is 2-7, m is a number 2-3 and R2 and R3 is independently xe2x80x94CH2CH2OH, xe2x80x94CH2CH(CH3)OH or an alkyl group with 1-5, preferably 1-3 carbon atoms. N,N-Dimethylethanolamine esters of this type have been described in e.g. U.S. Pat. No. 4,228,042, where they were used as intermediates to produce quaternary surfactants for use in laundry detergent compositions.
Other suitable examples of compounds according to the present invention are the amidoamines described by the formula (III): 
where R5 is an alkyl group containing 7-21, preferably 7-17, carbon atoms. Such amidoamines have been described in EP-A2-0 265 824, where they were used as intermediates for zwitterionic phosphate ester surfactants for use in personal care, and also in DT-A1-2641286, where they were used as intermediates for quaternary ammonium compounds for use as impregnating agents for cellulose fibre materials.
In formulations containing an active amount of the amino compounds as an adjuvant, the amount of amino compound can vary within wide limits, but is normally from 5% to 500% by weight calculated on the amount of pesticide or fertilizer present in the formulation, preferably between 10% to 200%, and most preferably between 15% to 80%.
The product (II) may easily be produced by reacting an ethercarboxylic acid according to formula (IV), 
where R4 and n have the meaning mentioned above for formula II, with an alkanolamine such as N-methyldiethanolamine, triethanolamine, 3-dimethylamino-1-propanol or N,N-dimethylethanolamine. Suitable examples of hydrophobic groups R4 in formula IV are 2-ethylhexyl, octyl, decyl, coco alkyl, lauryl, oleyl, rapeseed alkyl and tallow alkyl.
The product (III) may easily be produced by reacting a fatty acid, or the methyl ester of a fatty acid, with N,N-bishydroxyethyl-1,3-propylenediamine. Suitable fatty acids are 2-ethylhexanoic acid, octanoic acid, decanoic acid, coco fatty acid, lauric acid, rapeseed fatty acid, oleic acid and tallow fatty acid. The product based on coco fatty acid is most preferred.
Suitable processes for the production of the amidoamine compounds (III) are described in e.g. WO 98/47860, DT-A1-2641286 and EP-A2-0 265 824.
The present invention also relates to certain compounds which are novel. These compounds have the formula (II), where R4 is an alkyl group containing 8-22, preferably 8-18, carbon atoms, n=2xe2x88x927, m is 3 and each R2 and R3 independently of each other is an alkyl group with 1-5, preferably 1-3, carbon atoms, or the formula (II), where R4 is an alkyl group containing 8-22, preferably 8-18, carbon atoms, n=2xe2x88x927, m is 2, one of the groups R2 and R3 is xe2x80x94CH2CH2OH or xe2x80x94CH2CH(CH3)OH and the other group is an alkyl group with 1-5, preferably 1-3, carbon atoms, xe2x80x94CH2CH2OH, or xe2x80x94CH2CH(OH3)OH or the formula (III), where R5 is CH3(CH2)3CH(CH2CH3)xe2x80x94.
The amino compounds of the present invention could be added as adjuvants to both liquid, such as aqueous, and solid agricultural compositions containing pesticides, such as herbicides, acaricides, fungicides and insecticides, as well as plant growth regulators and fertilizers. The liquid composition could be in the form of a solution, a microemulsion, an emulsion or a suspension. Typical examples of herbicides are different amine salts of glyphosate, such as the isopropylamine salt, the dimethylamine salt and the ethylenediamine salts; other salts of glyphosate, such as the sesquisodium salt and the trimethylsulphonium salt; glufosinate, salts of 2,4-dichlorophenoxyacetic acid, salts of 4-chloro-2-methylphenoxyacetic acid, bialaphos, dicamba, diphenylethers, imidazolinones and sulphonyl ureas. The amino compounds of the present invention are excellent adjuvants for the water soluble herbicides, e.g. the widely used herbicide glyphosate (glyphosate=N-(phosphonomethyl)-glycine), and the salts thereof. Suitable examples of fungicides are e.g. azoxystrobin, epoxiconazole, kcresoximmethyl and propiconazole.
Other examples of formulations where the amino compounds may be used as adjuvants are micronutrient solutions containing one or several micronutrients, such as iron, manganese, copper, zinc, boron and molybdenum. The micronutrients may be complexed to e.g. aminocarboxylates, such as EDTA, DTPA, HEDTA, EDDHMA and EDDHA. In addition to micronutrients and chelating agents, the formulations may also contain macronutrients, such as nitrogen, phosphorus, potassium, magnesium and sulphur, and pesticides may also be included. These above-mentioned formulations are particularly suitable for foliar applications.
The formulations according to the invention may also contain other additives, such as other surfactants, hydrotropes and preservatives; additives to further enhance pesticidal activity, such as ammonium sulphate; solvents, corrosion inhibitors, thickeners, sequestering agents, anti-freeze agents, anti-foam agents, anti-gelling agents and dyes.
The compositions could also contain viscosity reducing agents such as glycerol, ethylene glycol, propylene glycol and low molecular weight polyethylene or polypropylene glycols.
The compositions could be concentrates as well as diluted, xe2x80x9cready to usexe2x80x9d, solutions. The concentrations may vary within wide limits, and a pesticide formulation could contain 0.01-99.9% by weight of a pesticide, 0-40% by weight of ammonium sulphate and an amount of 0.01-70% by weight of an amino compound according to the invention. A suitable herbicide is glyphosate, or a salt thereof, which is preferably present in an amount of 0.02-70% by weight. An adjuvant according to the present invention can also advantageously be used in combination with solid agrochemical substances such as strobilurin analogues 
wherein R6 is an aromatic or heteroaromatic substituted or unsubstituted group, R7 is H or C1-C10 alkyl, A is CH or N and B is O or NH (e.g. azoxystrobin) and sulphonyl ureas to form granules or dispersions. The stability of the dispersions may be further enhanced by the addition of other conventional surfactants, such as nonionics, e.g. ethoxylated fatty alcohols or amines, or alkyl glycosides containing more than 10 carbon atoms in the alkyl chain. As a concentrate, the concentrations are normally in the range of 4-70% for the pesticide, 2-50% for the adjuvants and 0-40% of ammonium sulphate, whereas for the ready-to-use solutions the corresponding ranges are 0.01-4%, 0.01-8% and 0-40%. The components could all be mixed in the concentrate or be tank-mixed just before spraying the solution.
A fertilizer formulation could contain 0.0001-99.9%, preferably 0.001-99.9%, by weight of a fertilizer and an amount of 0.0001-70%, preferably 0.001-70%, by weight of an amino compound according to the invention. In a ready-to-use formulation the concentration of micronutrients are usually in the lower area of the range.
The following examples are illustrative of the invention and are not to be construed as a limitation of the scope.